Textile treating composition and method



Patented Dec. '29, 1953 UNITED STATES TEXTILE TREATING COMPOSITION AND METHOD Robert Geoffrey Aickin, London, and Alick R. England, assignors to Munden,

Pontypool, British Nylon Spinne England, a British co rs Limited, Pontypool, mpany, and Shell Development Company, Emeryville, Calif., a corporation of Delaware No Drawing. Application October 9, 1950, Serial No. 189,284

Claims priority, application Great Britain October 13, 1949 3 Claims. 1

This invention relates to the sizing and oiling of textile filaments, and it is particularly directed to a treatment whereby such filaments are both sized as Well as oiled by the application af a single composition. The invention finds particular utility in connection with the treatment of synthetic linear polyamide (nylon) yarns.

In the production of knitted articles from yarns, it is frequently necessary to apply an adhesive coating which protects the yarns during the knitting operation and in the handling operations subsequent thereto. Such adhesive coatings are known as sizes and the application of them to the yarn is known as sizing. A satisfactory size must not only protect the fabric from snags and pulled threads, but must adhere well to the yarn and not accumulate on the needles and sinkers. ing softened prior to the knitting operation and must be readily removable prior to the dyeing of the knitted fabrics. A number of sizes have been proposed which possess the aforesaid characteristics in varying degree, and one which has gvien particularly good results with nylon yarns is compound from a polyvinyl alcohol derivative containin attached hydroxyl groups, generally in admixture with boric acid or other additives capable of increasing the water-sensitivity of the resin.

Once the sizing operation is complete, the conventional practice has been to apply a lubricant to the sized yarn surfaces in order to impart the requisite oiliness characteristics thereto. Since this lubricating step is normally performed as the yarn is packaged into a cone, the lubricants applied to the sized yarn are normally referred to in the art as coning oils. The nature of the coning oil to be used will vary depending on the nature of the yarn and of the sizing material applied thereto, as well as on the conditions to be encountered durin the knitting process. In the case of nylon yarns, however, good results have heretofore been obtained by using vegetable oil lubricants of the type of olive or teaseed oil.

It is apparent that the yarn treating process as described above would be greatly simplified if a composition were available which, on application to the yarn, would perform the functions of both the size as well as the conin oil. However, the many efforts heretofore made to provide such a composition have been largely unsuccessful, particularly as regards nylon yarns, since the admixture of materials having lubricant qualities with the sizing composition has been found to imp-air the quality of the resulting size while at the same Moreover, it must be capable of be- 7 time being generally ineifective even from the lubricant standpoint. As indicated, the problem is particularly difficult in the case of nylon yarns since the requirements of a proper size for such filaments are extremely critical.

It is, therefore, an object of the present invention to provide an improved textile filament coat- It is our discovery thatthe foregoing objects are achieved by coating the nylon or other textile filaments with a composition made up of a hydroxylated polyvinyl resin, mineral oil, soap and a partial ester of a polyhydric alcohol with a fatty acid containing more than -8 carbon atoms in the molecule. This composition has been found to be capable of impartin excellent size and oiliness characteristics to nylon as well as other yarns and textile forms through use of but a single coating operation, and with marked elliciency and economy in the working up of the material.

The expression hydroxylated polyvinyl resin, as employed herein and in the appended claims, is intended to embrace those water-soluble or water-disp-ersible polyvinyl compounds or polyvinyl derivative compounds containing hydroxyl groups. Thus, the expression covers the partial esters of polyvinyl alcohol such as the partial acetates (partially saponified polyvinyl acetates being known in the trade as polyvinyl alcohol), the partial propionates, the partial butyrates, the partial formates, and the esters, Whether partial or not, formed by polyvinyl alcohol with glycolic, lactic or other hydroxy acids. The term also includes the various hydroxy-containing ethers, acetals and ketals of polyvinyl alcohol as, for example, the glycol ethers, the glycolic acid ethers, the partial formal, the partial acetal, the partial glyoxyl, the partial propional, the partial butyral and the ethyl-methyl ketal. Other representative hydroxylated polyvinyl resin compositions are those formed on the interpolymerization of partial polyvinyl esters with minor proportions of other polymerizable compounds such as vinyl chloride, maleic anhydride, unsymmetrical dichloroethylene, methylmethacrylate and the like. Also suitable for use in the present invention are the hydroxylated polyvinyl esters formed on the partial hydrolysis of such compounds as .vinyl chloride-vinyl acetate co-polymers, for example. In general, the hydroxylated polyvinyl resins under consideration are those Bin which Ifromabout 1 to 50% of the carbon atomsof the polyvinyl chain are attached to hydroxyl groups, or which otherwise contain an equivalentnumber .ofahydroxyl groups.

The mineral oil component of the composition is preferably a highly refined. .mineral oil :having a viscosity within the range of from about 40 to 400 seconds as measured by the Redwoooll instrument at 70 F. The class of 'oils known as technical white oils is especially useful since such oils have excellent stability and resistance to the development of odor and color on being stored or exposed to light. If desired, the mineral .oil fractionof the composition may be a compounded .oil, e. g., a mixture of a mineral lubricating oil with a fatty oil such as olive or teaseed oil, and the term mineral oil, as employed here and in the claims, is intended to embrace such cornpounded oils as well as mineral oils per se.

The soap employed in the composition may be any anionic detergent. Representative soap compositions are the sodium and potassium-salts of ,oleic or stearic acid or .of a sulphonated oil, sulphated alcohol or alkylaryl sulphonic acid. Particularly useful soaps are the oil-soluble, alkali metal (e. g sodium and potassium) naphthasulphonates, -i. e. the oil soluble sulphonates obtained by treatment of petroleum oils with oleum or concentrated sulphuric acid. Mixtures of soaps maybe employed, if desired.

The remaining essential component of the present composition-,is-a partial ester derived from a polyhydric alcohol and a fatty acid containing more thanB carbon atoms in the molecule.

Representative polyhydric alcohols which may be employed in forming such esters are glycol, glycerol, erythritol, =pentaerythritol, mannitol, sorbitol, and sorbitan, the latter compound being a partially dehydrated sorbitol. Representative fatty acid compounds which may .be en ployed in forming the partial esters are oleic acid recinoleic, palmiticacid, stearic acid, lauric acid, or one or more of the acids derived from neats-foot, olive, palm, peanut, coconut, castor, cottonseed, or like oils. Specific examples of these partial esters are glycerol mono-oleate, glycerol .di-oleate, sorbitan mono-stearate, sorbitan mono-oleate, glycol monopalmitate, and the glycerol mono-ester of the fatty acids of arachis oil.

In addition to the above mentioned essential ingredients, the composition of the present invention may contain other componentsas well. For example, there is preferably added a quantity of boric acid, barium chloride or other inorganic compound having the ability to modify the water-sensitivity of the .hydroxylated polyvinyl resin, together with a compound known to improve the running qualities of sizing solutions, representative compounds of this variety being the polymethacrylates, the polymers of the dioxolanes or alkylene oxides, and the water-soluble alkylol urea formaldehyde resins. Further, the composition may contain an anti-oxidant, particularly if thecomposition is to be subjected to prolonged storage. Thus, such anti-oxidants .agents beingmorpholine, morpholine nitrite, pyridine and sodium nitrite.

The composition of the present invention is applied to the yarns or other filaments under treatment :in the form of a solution, emulsion, suspension, or other liquid system. Thus, good .resultsarepbtained 1n the case of Water solutions-containing from about 3 to 12% of the hydroxylated polyvinyl resin and from about 3 to 17% mineral oil, from about 0.05 to 5% soap, and from about 0.1 to 5% of the partial ester of :the polyhydric alcohol with a higher fatty acid, the latter component being present in an amount not to exceed 30% of the mineral oil present. When boric acidor a compound having a'similar function is employed-the same is normally used in the amount of about 5 to 40% based on the weight of ,hydroxylated polyvinyl resin present. These same proportions apply with equally good results when solvents other than water are employed either in whole or in part.

The sizing-lubricant solutions to be applied to the yarns may be prepared in any desired fashion. However, the preferred method is first to form a water solution vfor dispersion) of the hydroxylated polyvinyl resin, together with any boric acid, barium chloride or similar additive, and then to .add the other components of the composition with .sufiicient agitation to insure the formation of an emulsion. The pH of the solution, as finallyprepared, preferably lies within the range of from about i to 6.5. Accordingly, since certain of the soaps employed may give an alkaline reaction on being-added to the aqueous resin solution or dispersion, ,it may be necessary to adjust the pH to the proper range by the additionof acetic acid or other weak acid to the mixture.

The size-oil compositions of this invention may be used in the simultaneous sizing and oiling of any textile materials which require such treatments, but they are particularly useful for the 'reatrnent of multi-filament nylon yarn. Nylon yarns, sized and oiled in accordance with this invention, .knit well and produce sheer full-fashioned stocking fabrics which are remarkably free from snags and pulled threads. Yarns derived from other water-insensitive synthetic linear polymers, such as polyvinyl chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl ester interpolymers, polymethacrylic esters, polyacrylonitrile, polyethylene and condensation products of .polycarboxylic acids and polyhydric alcohols or alkyleneoxides mayalso be sized and oiled by the compositions-of this invention. These compositions mayalso find application in the treatment .of natural textile materials such as cotton, silk, wool and linens and of artificial fibres derived fromcellulose, such as rayon. Moreover, while the size-oil compositions are particularly applicable in preparing yarn for full-fashioned knitting, they are also applicable in the circular knittingof fabrics from yarns and with other textile forms, such ,as films, staple fibres, and ribbons.

The invention is illustrated by the following examplesin which the partsare parts by weight.

Example I To a solution containing 8.0 parts of partially saponified polyvinyl acetate (saponification value 140, viscosity of 14.5% aqueous solution 90 centistokes at 25 0.), 1.6 parts boric acid and 90.4 parts water are added 8.0 parts of an oil composition containing 91.8% by weight of a solvent refined high viscosity index parafilnic lubricating oil having a viscosity of 320 seconds Redwood I at 70 F. and a flash point of 405 F., 5.0% by Weight of glycerol dioleate, 3.0% by weight of sodium naphthasulphonate and 0.2% by weight of 2,4-dimethyl-G-tertiary-butyl phenol. During the addition of the oil composition the mixture is continuously stirred so that a good emulsion results. The pH of the emulsion is gradually reduced to 5.5 at 20 C. by the addition of a small quantity of glacial acetic acid. The viscosity of this acidified emulsion is 26.9 centistokes at 25 C. The size-oil emulsion prepared in this manner is applied on. a single-end sizing machine to 30 denier filament nylon yarn which had been previously thrown to 30 s turns per inch and twist set. During the application the size-oil emulsion is continually circulated through the trough of the machine at a fiow rate of 200 millilitres per minute. The yarn after conditioning in a humid atmosphere contains 5.9% of size, of which 2.8% is oil. The conditioned yarn is coned without addition of further oil. The coned yarn is knitted on 54 gauge full-fashioned hosiery knitting machines. The yarn as it is removed from the cone is passed through a trough of water containing, if desired, wetting agents to soften the size. The yarn runs easily through the needles of the knitting machine and the fabric produced has good stitch formation and high snag resistance and is very easy to scam. The composition is readily removed from the knitted fabric by treatment in hot water.

Example II A size-oil emulsion prepared as in Example I, and containing additionally 0.8% by weight of Carbowax 1500, a polyethylene glycol having the general formula and an average molecular weight between 500 and 600 which is produced and marketed by Carbide and Carbon Chemicals Corporation, is applied on a single-end sizing machine to 30 denier 10 filament nylon yarn containing threequarters 8 turns per inch. During the application the emulsion is circulated through the machine troughs at a flow rate of 200 millilitres per minute. The sized yarn contains 6.4% of size of which 2.6% is oil. The yarn is conditioned in a humid atmosphere and is wound onto doubleended bobbins and up-twisted to 30 8 turns per inch. The thrown yarn is twist-set for 1 hours in a cabinet at 108 F. dry-bulb temperature and a 170 F. wet-bulb temperature. The twist-set yarn is coned on a conventional machine without the addition of further oil. The coned yarn is knitted on a 54 gauge full-fashioned hosiery knitting machine, the yarn running through a trough of water to soften the size. The fabric produced has good stitch formation, high snag resistance and is easy to scam. Similarly, when the sized yarn twisted and coned as above is knitted on a 340 needle seamless hosiery knitting machine, the hose produced has good snag resistance and stitch formation.

Example II] To a solution containing 8.0 parts of partially saponified polyvinyl acetate (saponification value 140, viscosity of a 14.5% aqueous solution centistokes at 25 C.) 1,6 parts of boric acid and 90.4 parts of water are added 8 parts of oil composition containing 91.8% by weight of a solvent refined high viscosity index parafiinic lubricating oil having a viscosity of 320 seconds Redwood I at 70 F. and a flash point of 405 F., 5.0% by weight of glycerol mono-oleate, 3.0% by weight of sodium naphthasulphonate and 0.2% by weight of 2,4-dimethyl-6-tertiary butyl phenol. During the addition of oil the mixture is continuously stirred so that a good emulsion results. The pH of the emulsion is gradually reduced to 5.8 by the addition of a small quantity of glacial acetic acid. The acidified emulsion has a viscosity of 22.9 centistokes at 25 C. The size-oil composition is applied on a single-end sizing machine to 30 denier 10 filament nylon yarn which had been previously thrown to 30 8 turns per inch and twist-set. After conditioning in a humid atmosphere the sized yarn is found to contain 4.9% size, of which 2.3% is oil. The yarn is coned without the addition of further oil. The coned yarn is knitted on 54 gauge fullfashioned hosiery knitting machines. The resulting fabric has good snag resistance and excellent stitch formation.

The saponification number of the partially saponified polyvinyl acetate represents the number of milligrams of potassium hydroxide required to completely saponify one gram of the partially saponified polyvinyl acetate material employed.

The various percentages employed herein are on a Weight basis unless otherwise indicated.

We claim as our invention:

1. A composition of matter suitable for the simultaneous sizing and oiling of textile filaments comprising an aqueous emulsion of about 3 to 17% of mineral oil in admixture with from about 3 to 12% of a water-soluble hydroxylated polyvinyl resin, from about 0.05 to 5% of anionic detergent,.from about 0.15 to 4.8% of boric acid, and from about 0.1 to 5% of the partial ester of a polyhydric alcohol with a fatty acid containing more than 8 carbon atoms in the molecule, said partial ester being present in amount not exceeding 30% of the mineral oil present and said composition having a pH within the range of 4.0 to 6.5.

2. A composition as defined in claim 1 wherein the resin is partially saponified polyvinyl acetate.

A composition as defined in claim 2 wherein the mineral oil has a viscosity within the range of 40 to 400 sec. Redwood I at 70 F.

ROBERT GEOFFREY AICKIN. ALICK R. MUNDEN.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMPOSITION OF MATTER SUITABLE FOR THE SIMULTANEOUS SIZING AND OILING OF TEXTILE FILAMENTS COMPRISING AN AQUEOUS EMULSION OF ABOUT 3 TO 17% OF MINERAL OIL IN ADMIXTURE WITH FROM ABOUT 3 TO 12% OF A WATER-SOLUBLE HYDROXYLATED POLYVINYL RESIN, FROM ABOUT 0.05 TO 5% OF ANIONIC DETERGENT, FROM ABOUT 0.15 TO 4.8% OF BORIC ACID, AND FROM ABOUT 0.1 TO 5% OF THE PARTIAL ESTER OF A POLYHYDRIC ALCOHOL WITH A FATTY ACID CONTAINING MORE THAN 8 CARBON ATOMS IN THE MOLECULE SAID PARTIAL ESTER BEING PRESENT IN AMOUNT NOT EXCEEDING 30% OF THE MINERAL OIL PRESENT AND SAID COMPOSITION HAVING A PH WITHIN THE RANGE OF 4.0 TO 6.5. 